Methods of making novel colorants for use within ink systems

ABSTRACT

Novel addition products of hydroxyl-protecting groups (such as isocyanates) with oxyalkylene-substituted intermediates, such as poly(oxyalkylenated) aniline compounds, for the eventual production of substituted, and substantially pure, colorants, particularly diazo and triphenylmethane derivatives, through the reaction of such intermediates with certain reactants are provided. These new colorants exhibit improved wax and/or oil solubility and high purity, particularly due to the inability of certain impurities to deleteriously react with the protected hydroxyl groups of either the intermediate or the colorant during and/or after formation thereof. A method for producing such novel colorants through utilization of these novel substantially pure colorant intermediates is also provided.

FIELD OF THE INVENTION

This invention relates to novel addition products of hydroxyl-protectinggroups (such as isocyanates) with oxyalkylene-substituted intermediates,such as poly(oxyalkylenated) aniline compounds, for the eventualproduction of substituted, and substantially pure, colorants,particularly diazo and triphenylmethane derivatives, through thereaction of such intermediates with certain reactants. These newcolorants exhibit improved wax and/or oil solubility and high purity,particularly due to the inability of certain impurities to deleteriouslyreact with the protected hydroxyl groups of either the intermediate orthe colorant during and/or after formation thereof. A method forproducing such novel colorants through utilization of these novelsubstantially pure colorant intermediates is also provided.

BACKGROUND OF THE PRIOR ART

All U.S. patents cited within this specification are hereby incorporatedby reference.

Wax-based and/or oil-based ink and ink-jet systems require compatiblecolorants therein to provide the most effective and reliable printingresults. Derivatives of poly(oxyalkylenated) dyes and/or colorants areparticularly desired for these end-uses because of their miscibility,high color strength characteristics, as well as ease in handling liquidcolorants of this nature. The hydroxyl groups of suchpoly(oxyalkylenated) colorants and/or dyes are susceptible toadventitious attack by Lewis acids and bases present within the reactionmedium. Unfortunately, such an attack renders the colorant unreactive,and incapable of modifications designed to tailor wax- and/oroil-solubility or compatibility. Such unreactive, residual species aregenerally present as impurities in the desired colorants. Such unwantedreaction products create undesirable possibilities of reduced colorantsolubilities, viscosity modifications, weakening of color strengths, andother like problems, such as discussed within certain prior artreferences, including U.S. Pat. No. 5,782,966 to Bui et al., and U.S.Pat. No. 5,637,638 to Chandler et al., as well as European PatentApplication 769,509 to Banning et al. Such references indicate theproblems associated with typical prior art processes for manufacturingcertain dyes (including wax-based ink types) and/or colorants. Thus,removal or, more importantly, avoidance of ways to generate theseunreactive species is absolutely necessary for providing reliable andeffective dyes and/or colorants for such end-use applications. Theseprior art references illustrate ways to tailor the desired physicalproperties via the reaction of isocyanate with the dyes and/or colorantsthemselves after formation of such compounds. Unfortunately, such areaction modifies the colorants as long as they are reactive. It has noeffect on colorants that have been rendered unreactive. Such a syntheticroute would therefore always produce unwanted unreactive impurities thatare detrimental to the performance of these products in the desired inksystems. A more reliable process and thus a more reliable dye and/orcolorant compound is thus necessary to provide the industry with a highcolor strength, optimum viscosity, high purity dye and/or colorant,particularly within wax-based and/or oil-based ink applications. Theprior art teachings have not provided a sufficiently consistent solublewax-based dye and/or colorant due to these adventitious reactionproblems. The costs involved in purification necessary to ensure thefinished dye and/or colorant is viable and not off-quality have provenexcessive enough to merit the need for even greater improvements withinthis technological field.

Examples of polyoxyalkylene substituted colorants include those taughtwithin U.S. Pat. No. 5,919,839, and EP 0 896 038 A2 describe phasechange, or hot melt inks utilizing the reaction product of an isocyanate(e.g., octadecyl isocyanate) and hydroxyl containing colorant to form acolored urethane wax. Other examples of such reactions include U.S. Pat.No. 5,919,846 and PCT patent Application WO 94/14902 (all describing thereaction of hydroxyl containing colorants with mono and diisocyanates).These colorants, in order to be utilized within such hot melt inksystems require high purity and complete compatibility within thewax-based ink system. The presence of electrophilic species, in thiscase, phthalates for example, in the urethane substituted xanthenecolorants reduces the compatibility of these colorants in such wax basedink systems. U.S. Pat. No. 4,833,197 describes an offset ink usingdiluents, for example, mineral oils with a boiling range of 200°-350°C., and no more than 20% of aromatic components. Again, however,electrophilic phthalates present within the urethane-substitutedxanthene colorants remain insoluble in these diluents, thus making thesecolorants unsuitable for use in these applications. Such a problem isinherent as well with other electrophiles.

Thus, even though poly(oxyalkylenated) dyes and/or colorants have onlyrecently been made available to the wax-based ink market, theutilization of such colorants, particularly made from certainpoly(oxyalkylenated) intermediates and other reactants, has still beenlimited due to the lack of complete compatibility in wax and/or oilbased systems due to the formation of the aforementioned deleteroiuselectrophile-hydroxyl reaction products. There thus exists a need toimprove upon this procedure and ultimately to produce a novelintermediate which provides the ability of forming highly desirabledenivatized oxyalkylenated dyes and/or colorants but does not require amulti-step process in forming the intermediate alone which furthermoreprecludes the formation of deleterious phthalates. To date, the priorart has not accorded such an improvement within this specific area ofcolorant chemistry. Because of the lack of such a specific type of dyeand/or colorant intermediate, the versatility and widespread use of suchcolorants in different types of inks and substrates has not beenavailable. There is thus a need to provide wax-based and/or oil-basedink-jet colorants and compositions that are readily and consistentlysoluble due to reduction of electrophilic reaction products. To date,there have been no improvements for such wax-based dyes and/or colorantsreducing the possible production of deleterious electrophile impuritiesthus permitting consistent use within, as one possible end-use,wax-based ink-jet inks.

OBJECTS OF THE INVENTION

Therefore, one of the objects of the invention is to provide athoroughly wax- and/or oil-soluble urethane-substituted dye and/orcolorant. Another object of this invention is to provide a syntheticroute for such a dye and/or colorant wherein all reactive sites aresubstituted with hydroxyl-protecting groups, such as urethanes, ethers,diurethanes, and combinations thereof. Another object of the inventionis to provide a specific urethane substituted aniline intermediate forthe production of a urethane substituted dye and/or colorant. Stillanother object of the invention is to provide an intermediate that is anaddition product of poly(oxyalkylene)aniline and an isocyanate for usein the manufacture of dyes and/or colorants, for instancepoly(oxyalkylenated) diazo or triphenylmethane colorants. A furtherobject of the invention is to provide an addition product of anisocyanate with a polyoxyalkylenated aniline intermediate which willalternatively form a dyestuff and/or colorant upon reaction withselected reactants and cannot be readily attacked by electrophilicgroups and/or impurities within the reaction medium, and thus providesexcellent yield of the desired colorant alone. Yet another object ofthis invention is to provide a relatively inexpensive method forproducing such beneficial urethane-substituted dyes and/or colorants.

Accordingly, this invention encompasses an aniline or substitutedaniline derivative intermediate comprising at least one constituentselected from the group consisting of urethanes, ethers, diurethanes,and any combinations thereof, wherein said at least one constituent is acapped moiety further comprising from about 2 to about 200 molesoxyalkylene groups having from 2 to 18 carbon atoms, glycidol, glycidyl,and any combinations thereof, and wherein said constituent is solelybonded to any amine groups present on said aniline derivativeintermediate. The term “aniline derivative” is intended to encompass anyphenyl-based compound with at least one nitrogen atom bonded directly tothe phenyl moiety and that does not also include a hydroxyl group bondeddirectly to the phenyl moiety (and thus is not an aminophenol).

Such hydroxyl-protecting groups include, but are not limited to reactionproducts of the terminal hydroxyls on the oxalkylene, glycidol, orglycidyl groups and compounds such as isocyanates, acid halides, acidanhydrides, diisocyanates (further reacted with an alcohol to form adiurethane), and the like, as well as mixtures thereof. Isocyanates aremost preferred thereby forming urethane-based colorants after reactionbetween the hydroxyl and the isocyanate itself The purpose for thepresence of such groups is noted in greater detail below, but the term“hydroxyl-protecting group” or its plural form is intended to encompassany of such urethane, ether, or diurethane pendant groups present toprevent attack of the terminal hydroxyls by electrophilic species orother impurities within the reaction medium and which is not susceptibleto attack itself (and thus removal from the hydroxyl moieties) by thesame electrophiles and/or impurities. In such a manner, the desiredcolorants exhibit the characteristics desired of polymeric[poly(oxyalkylenated)] colorants without the potential problemsassociated with attack on such free hydroxyls.

Since the oxyalkylene groups as noted above, as well as any otherpotential hydroxyls present on the ring, are reactive, the reaction witha certain amount of such hydroxyl-protecting groups [e.g., isocyanatesand diisocyanates (such as, without limitation, alkyl types, includingoctadecyl isocyanate, n-butyl isocyanate, and the like, and phenyland/or subsituted phenyl types, including without limitation, toluenediisocyanate, and the like)] produces the desired protected pendantgroups (e.g., urethane moieties) thereon. Most preferably, at least twohydroxyl-protecting groups (and thus, for example at least two urethanegroups) are present. As one example, the most preferred intermediatecompound encompassed within this invention conforms to the structure ofFormula (I)

wherein R₁, R₂, R₃, and R₄ are either the same or different andrepresent hydrogen, hydroxyl, halogen, such as Cl, Br, or F, C₁-C₄alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylsulfonyl, C₁-C₄ alkylsulfamoyl, C₅-C₆cycloalkylsulfamoyl, nitro, cyano, carbomoyl, trifluoromethyl, C₁-C₄alkoxycarbonyl, C₁-C₄ alkanoyl, C₁-C₄ alkylcarbamoyl, phenoxy,phen(C₁-C₄)alkoxy, phenylcarbamoyl, phenylsulfonyl, phenylsulfamoyl,benzoyl, or phenylazo groups, with each group optionally subsituted withhalogens or C₁-C₄ alkyl or C₁-C₄ alkoxy groups; wherein x+y is greaterthan 0 and less than 4; wherein R′ is selected from the group consistingof C₁-C₁₀ alkoxy, C₁-C₁₀ polyoxyalkoxy, C₁-C₁₀ alkylester, and C₁-C₁₀alkyl; wherein R″ is selected from the group consisting of hydrogen andC₁-C₄ alkyl groups; and wherein R′″ is selected from the group selectedfrom hydrogen, C₁-C₂₄ alkyl groups, phenyl, substituted phenyl, and anycombinations thereof. Preferably R′ is H, methyl, ethyl, Cl, Br or I, R″is hydrogen, methyl, or ethyl, and R′″ is hydrogen, methyl, or ethyl. Ina more preferred embodiment, the aniline derivative intermediate issubstituted with methyl or ethyl, or is unsubstituted, i.e. R₁, R₂, R₃,and R₄ are all H. The intermediate is prepared from aniline which isreacted with from 2 to 200 moles of at least one constituent selectedfrom the group of oxyalkylenes having from 2 to 18 carbon atoms,glycidol, and glycidyl, and any combinations thereof, wherein saidconstituent is solely bonded to the amine. It should be evident to theordinarily skilled polymeric colorant artisan that addition of specificchain lengths of such oxyalkylene monomers is imperfect and thus thenumber of moles present thereon such an aniline-based compound isindicative of the average number of moles added, and not the specificnumber. Preferably, R′″ is selected from C₁-C₂₄ alkyl, more preferablyfrom C₄ to C₁₈.

Furthermore, the inventive colorants produced by the reaction of certainreactants with this specific type of intermediate include diazos,triphenylmethanes, and the like, preferably conforming with thefollowing structures (II), (III), and (IV):

wherein for each of (II), (III), and (IV), above, R′ is selected fromthe group consisting of hydrogen and C₁-C₂₀ alkyl; wherein R″ isselected from the group consisting of hydrogen, C₁-C₁₀ alkoxy, andC₁-C₂₀ alkyl; wherein R′″ is selected from the group consisting ofhydrogen, C₁-C₄ alkyl groups; and wherein R′″ is selected from the groupselected from hydrogen and C₁-C₂₄ alkyl groups; or any salts thereof(such as salts with inorganic or organic anions, including, withoutlimitation, halides, sulfonates, hydrogen sulfonates, methylsulfates,and the like).

Such an aniline intermediate in Formula (I) is useful in producing thecolorants of Formulae (II), (III), and (IV).

DETAILED DESCRIPTION OF THE INVENTION

The amino group of said aniline is di-substituted with an additionproduct of an isocyanate and a poly(oxyalkylene) substituent having astraight or branched polymer chain selected from oxyalkylene oxide,glycidyl, and glycidol. In one embodiment, at least one mole of theurethane-substituted aniline is reacted with phthalic anhydride or otheraromatic compound having an aldehyde functionality available. A secondmole of urethane substituted aniline may also be provided to form atriphenylmethane colorant. This novel intermediate has the advantagethat colorants made from the intermediate is totally compatible in thewax-based and/or oil-based ink systems, and that colorants of variousfamilies, such as diazos, triphenylmethanes, methines, and the like, canbe produced from this intermediate. Thus, reactants utilized to producesuch novel colorants include, without limitation, diazonium salts,aminobenzaldehydes, diazotized compounds, and the like, which would beclearly appreciated by the ordinarily skilled artisan within thecolorant industry (the term “colorant” is intended to encompass anycompound which absorbs in the visible spectrum).

In particular, it is highly desirable to provide a method of forming anaddition product of an isocyanate with a specific polyoxyalkylenatedaniline intermediate. Furthermore, the aniline intermediate encompassedwithin this invention thus comprises from 2 to about 200 moles,preferably, from 3 to about 100, more preferably from about 3 to about50, and most preferably from about 3 to about 10, of at least oneconstituent selected from the group of oxyalkylene groups having from 2to 18 carbon atoms, alkoxy alkylester groups having from 2 to 18 carbonatoms, glycidol, and a glycidyl group wherein said constituent is solelybonded to the amine, and any free hydroxyls are reacted with isocyanatesuch as octadecyl isocyanate. Such a method of producing the additionproduct of an isocyanate with such a specific oxyalkylenated anilineintermediate is also contemplated within this invention as well. Theamine constituent may reside in any position relative to other pendantgroups (such as straight or branched alkyl chains, straight or branchedalcohol chains, and the like) on the benzene ring (i.e., p-toluidine,o-toluidine, m-toluidine, p-anisidine, o-anisidine, or m-anisidine);however, aniline and m-toluidine are preferred. Thus, the preferredaniline intermediate is also contemplated within this invention as isthe method of making such a compound, as defined by the FIGURE (I),above. Such a method comprises the reaction of from 2 to 200 moles of atleast one compound selected from the group consisting of an alkyleneoxide having from 2 to 18 carbon atoms and glycidol with m-aniline at atemperature of from about 120 to about 250° F. The invention also coversthe actual compound of Formula (I), above as well. Preferably R above(for both I and II) is hydrogen, C₁₋₄ alkoxy, or C₁₋₄ alkyl; mostpreferably R′ is hydrogen. Also, preferably R″ is methyl or ethyl (mostpreferably methyl), and R″ is preferably H. R″ is selected from thegroup consisting of C₁-C₂₄ alkyl, preferably R″ is C₁₂-C₂₄ alkyl, mostpreferably R″ is C₈.

It is an advantage of the present invention that the urethanesubstituted dye and/or colorant can be design engineered to obtaindesired properties for specific printing platforms and architectures. Itis also an advantage, though not a requirement, of the present inventionthat the urethane substituted dye and/or colorant is very pure, beingfree of salts and other insoluble contaminants. It is another advantageof the present invention that the urethane substituted dye and/orcolorant can be used in combination with other ink carrier materials toobtain ink compositions that possess excellent spectral strengths. It isstill another advantage, though not a requirement, of the presentinvention that the urethane substituted dye and/or colorant issubstantially transparent. These and other aspects, features, andadvantages are obtained by the use of such inventive intermediates (suchas urethane-substituted anilines) to form such substituted colorantsthat are suitable for use with waxes and/or oils in phase change ink jetinks and offset inks that may be employed in direct or indirect printingapplications.

It has been found that the reaction of isocyanates with oxyalkylenatedaniline compounds and other reactants (as discussed above), ultimatelyresults in the formation of a dye and/or colorant substantially modifiedby the reaction of the nucleophilic hydroxyl groups of the intermediateand substantially free of unmodified, insoluble impurities, which arecompletely compatible in wax and/or oil systems. The structures (II),(III), and (IV) above are merely preferred embodiments of such a broadrange of possible dyes and/or colorants.

As noted above, such novel intermediates permit production of colorantsmade therefrom that are substantially modified by the reaction of thenucleophilic hydroxyl groups with isocyanates. A low amount of such anunwanted electrophile-hydroxyl reaction product may be produced on thefinal colorant product; however, such an amount is drastically reducedin comparison with the previously followed production methods withoutisocyanate-capped hydroxyl moieties of the inventive intermediate. Thus,the amount of unwanted eletrophile-hydroxyl reaction product provided bythe inventive method and thus found on the target dye and/or colorant isbelow about five to ten molar percent in total. Such an amount is thusthe definition of the term “substantially pure” as well.

Such inventive substantially pure urethane-based colorants may beutilized in any number of coloring procedures, including ink, paint,print, dye, tint, and the like, applications. Thus, compositionsutilized to provide colorations to various substrates, including,without limitation, cellulose-based substrates (paper, cotton fabrics,and the like), magazine-paper substrates, and the like, are preferredsurfaces for coloring. Other surfaces, substrates, etc., may becontacted with the inventive colorants as well, Most preferably,however, such colorants are to be utilized in ink applications, mostnotably inkjet, lithographic, and offset ink operations. The offsetprinting process is used to print newsprint, magazines, signage, andlike procedures and end-uses. In such operations, it is important toprovide long-term solution stability of the colorant within the targetink solution and water resistance of the printed image from the inkcomposition. For inkjet inks, particularly wax-based types, heatstability of the entire ink system is of paramount importance, since theprinting process comprises numerous periods of heating and coolingcycles in order for the inks to perform the desired print operation.Thus, such inks must be able to retain their color strength uponevaluation of exposure at 150° C. for prolonged and/or intermittentperiods (e.g., 30 minutes or 5 minutes heated, 5 minutes cooled, 5minutes heated, and so on, as merely examples). The color differencebetween an initial print and an oven-aged print is calculated using thefollowing equation:

ΔE*=((L* _(initial) −L* _(aged))²+(a* _(initial) −a* _(aged))²+(b*_(initial) −b* _(aged))²)^(½)

wherein ΔE* represents the difference in color between the initialprinted sample and the sample printed with oven aged ink. L*, a*, and b*are the color coordinates; wherein L* is a measure of the lightness anddarkness of the print sample; a* is a measure of the redness orgreenness of the print sample; and b* is a measure of the yellowness orblueness of the print sample. For a further discussion and explanationof this testing procedure, see Billmeyer, F. W., et al., Principles ofColor Technology, 2nd Edition, pp. 62-64 and 101-04. Thus, the inks mustexhibit a minimal change in color over such time (e.g., ΔE* of at most1.5).

For offset inks, and particularly heat-set inks, generally, suchcompositions include alkyds as heat-set inks used primarily aspigment-wetting vehicles (although they may also improve the stabilityof the ink, improve the gloss of the ink on the target substrate, andaffect water pick-up after contact with the desired surface). Highboiling petroleum distillates are utilized as the diluent/solventcomponents therein within such heat-set offset ink formulations. Otheradditives commonly found within such offset inks are polyethylene (slipagent), organic aluminum compounds (rheology modifiers), and lowmolecular weight micronized hydrocarbon resins (to increase ink tack).

For lithographic inks (cold set), generally, such compositions functionthrough penetration of the ink within the target substrate (e.g., paper,for example). Mineral oil or vegetable oils are utilized as carrierswithin such compositions with small amounts of varnish (typicallygilsonite or hydrocarbon-based resins, as examples) added to control thelithographic properties of the ink composition, with components, such asbentonite, for example, added for rheology control.

Wax-based inkjet inks are generally solid at room temperature andsubsequently heated to a temperature above its melting point andmaintained at a temperature above about 150° C. wherein the compositionmust exhibit fluid physical properties required for inkjet printingmethods. Thus, these inkjet ink composition generally comprise twocomponent types: colorants and vehicles for the colorants. The vehicleoften consists of a blend of polymers which function to control theviscosity temperature profile and balance the performance of the ink inthe printhead with the performance of the ink on the target substratesurface (e.g., again, paper). Such polymers tend to be based upon fattyacids, urethanes, and natural and/or synthetic waxes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Without limiting the scope of the invention, the preferred features ofthe invention are hereinafter set forth.

Intermediate Synthesis

EXAMPLE 1

100 parts of a polyoxyalkylene (with an average of 10 moles of ethyleneoxide present thereon) substituted aniline intermediate were chargedinto a reactor vessel with 111 parts of octadecenyl isocyanate, and 2.0parts of dibutyltindilaurate catalyst. The mixture was heated withstirring to 70° C. under a N₂ atmosphere. After 4.0 hours at 70 C anFT-IR spectrum of the product was obtained to insure all isocyanatefunctionality is consumed. The absence (disappearance) of a peak atabout 2275 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding tourethane frequencies, thereby confirm the conversion of the isocyanateto the urethane.

EXAMPLE 2

100 parts of the polyoxyalkylene (having an ethylene oxide to propyleneoxide ratio of about 1:1, and an average of about 5 moles of eachalkylene oxide present thereon) substituted aniline intermediate werecharged into a reactor vessel with 98 parts of octadecylisocyanate, and2.0 parts of dibutyltindilaurate catalyst. The mixture was heated withstirring to 70° C. under a N₂ atmosphere. After 4.0 hours at 70 C anFT-IR spectrum of the product was obtained to insure all isocyanatefunctionality is consumed. The absence (disappearance) of a peak atabout 2275 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding tourethane frequencies, thereby confirm the conversion of the isocyanateto the urethane.

Colorant Production

The general methods of making the preferred inventive colorants are asfollows:

EXAMPLE 3 Diazo—Yellow

135 parts of 98% sulfuric acid was charged to a flask containing 452parts of water followed by 111 parts of 3-chloroaniline and 12 parts of2-ethylhexanol. This mixture was allowed to stir for 0.5 hr. Separatelya mixture of 71.3 parts of sodium nitrite and 233 parts of water wasprepared in a beaker. This was charged to the flask slowly, keeping thetemperature of the contents in the flask between 0 and 5° C. After theaddition is complete, the contents were allowed to stir for 2 hourswhile maintaining a temperature between 0 and 5° C. In a separatebeaker, coupler was prepared by mixing 683 parts of the intermediateprepared in Example 1 with 683 parts of toluene. The diazonium salt inthe flask is added to the coupler slowly maintaining a temperature <10°C. After the addition is complete, the mixture is allowed to stir for 1hour. The acid is neutralized with a caustic solution, the productwashed with water, and dried. A UV/VIS spectrum of the bright yellowproduct shows a lambda max absorbance at 425 nm in toluene, and a halfheight band width of 120 nm.

EXAMPLE 4 Triphenylmethane—Blue

1000 parts of the intermediate from Example 1 was charged to a flaskcontaining 66 parts of p-dimethylaminobenzaldehyde and 14 parts of urea.To this mixture was charged 90 parts of muriatic acid over a 5 minuteperiod. This mixture was allowed to heat up to 95-105° C., andmaintained at this temperature overnight. At the end of the hold period,the reaction mixture was allowed to cool to 75° C., and 120 parts ofp-benzoquinone was added. The mixture was allowed to stir for 1.5 hrsmaintaining a temperature of 75-85° C. The acid is neutralized with acaustic solution, the product washed with water, and dried. A UV/VISspectrum of the bright mid range blue product shows a lambda maxabsorbances at 548 nm and 607 nm in toluene.

EXAMPLE 5 Diazo—Red

160 parts of 98% sulfuric acid was charged to a flask containing 117parts of water followed by 120 parts of acetic acid and 1 part of2-ethylhexanol. 38 parts of 2-aminobenzothiazole was added slowly toallow complete mixing. This mixture was allowed to stir for 0.5 hrmaintaining a temperature below 0° C. 95 parts of nitrosyl sulfuric acidwas added slowly to this mixture slowly maintaining a temperature<0° C.This mixture was allowed to stir for 2.5 hours maintaining a temperature0 and −5° C. At the end of the hold period, the diazotization iscomplete, and the diazo is added to a coupler prepared by mixing 167parts of the intermediate from Example 2 and 167 parts of toluenemaintaining temperature<10° C. After the addition is complete, themixture is allowed to stir for 1 hour. The acid is neutralized with acaustic solution, the product washed with water, and dried. A UV/VISspectrum of the bright red product shows a lambda max absorbance at 489nm in toluene, and a half height band width of 130 nm.

EXAMPLE 6 Ink Jet Ink

20 parts of the yellow colorant produced in Example 3 was mixed with acolor stick from Xerox for a Phaser™850 printer under heat (120-150°C.). The product was allowed to mix well while hot and poured into analuminum dish. This mixture was subjected to several heating and coolingcycles to determine compatibility through these cycles. The productappeared to be completely compatible with the wax systems throughout theheating/cooling cycles.

EXAMPLE 7 Offset Based Ink

5 parts of the blue colorant produced in Example 4 was mixed with a 98parts of the black offset base 1K-01967 from CPS. The product wascompletely compatible. The final mixture was used as an ink and drawndown on paper. The image on paper is a toned black (b value of 2.89 vs3.51 for untoned black base) and indicated that the individualcomponents of the ink were completely compatible.

There are, of course, many alternate embodiments and modifications ofthe present invention which are intended to be included within thespirit and scope of the following claims.

What is claimed is:
 1. A method of producing a colorant comprising thesteps of (a) providing an aniline derivative intermediate comprisingfrom about 2 to about 200 moles of at least one hydroxyl-containingconstituent selected from the group of oxyalkylene groups having from 2to 18 carbon atoms, glycidol, glycidyl, and any combinations thereof,wherein said at least one constituent is solely bonded to the amine; (b)reacting said aniline derivative intermediate of step “a” with at leastone hydroxyl-protecting-group-containing compound such that the terminalhydroxyl group of said at least one hydroxyl-containing constituent iscapped by a pendant group selected from the group consisting of aurethane, an ether, a diurethane, and any combinations thereof to form acapped aniline derivative intermediate; and (c) reacting said cappedaniline derivative intermediate of step “b” with at least one otherselected reactant in order to produce a colorant; wherein said colorantexhibits complete solubility within at least one solvent selected fromthe group consisting of ink jet ink waxes and offset ink oils.
 2. Themethod of claim 1 wherein said at least onehydroxyl-protecting-group-containing compound of step “b” is selectedfrom the group consisting of isocyanates, anhydrides, acid chlorides,diisocyanates, and any combinations thereof.
 3. The method of claim 2wherein said hydroxyl-protecting group capped aniline derivativeintermediate of step “b” conforms to the structure of Formula (I)

wherein R₁, R₂, R₃, and R₄ are either the same or different arerepresent hydrogen, hydroxyl, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄alkylsulfonyl, C₁-C₄ alkylsulfamoyl, C₅-C₆ cycloalkylsulfamoyl, nitro,cyano, carbomoyl, trifluoromethyl, C₁-C₄ alkoxycarbonyl, C₁-C₄ alkanoyl,C₁-C₄ alkylcarbamoyl, phenoxy, phen(C₁-C₄)alkoxy, phenylcarbamoyl,phenylsulfonyl, phenylsulfamoyl, benzoyl, or phenylazo groups, with eachgroup optionally subsituted with halogens or C₁-C₄ alkyl or C₁-C₄ alkoxygroups; wherein x+y is greater than 0 and less than 4; wherein R′ isselected from the group consisting of C₁-C₁₀ alkoxy, C₁-C₁₀polyoxyalkoxy, C₁-C₁₀ alkylester, and C₁-C₁₀ alkyl; wherein R″ isselected from the group consisting of hydrogen and C₁-C₄ alkyl groups;and wherein R′″ is selected from the group selected from C₄-C₂₄ alkylgroups, phenyl, substituted phenyl, and any combinations thereof.
 4. Themethod of claim 3 wherein R₁, R₂, R₃, and R₄ are the same or differentand are selected from the group consisting of hydrogen, hydroxyl,methyl, ethyl, Cl, Br, and I; wherein R″ is selected from the groupconsisting of hydrogen, methyl, and ethyl; and wherein R′″ is selectedfrom the group consisting of any of C₄-C₁₈ alkyl.
 5. The method of claim1 wherein said at least one other selected reactant of step “c” isselected from the group consisting of at least one diazonium salt, atleast one aminobenzaldehyde, at least one diazotized compound, and anymixtures thereof.
 6. The method of claim 2 wherein said at least oneother selected reactant of step “c” is selected from the groupconsisting of at least one diazonium salt, at least oneaminobenzaldehyde, at least one diazotized compound, and any mixturesthereof.
 7. The method of claim 3 wherein said at least one otherselected reactant of step “c” is selected from the group consisting ofat least one diazonium salt, at least one aminobenzaldehyde, at leastone diazotized compound, and any mixtures thereof.
 8. The method ofclaim 4 wherein said at least one other selected reactant of step “c” isselected from the group consisting of at least one diazonium salt, atleast one aminobenzaldehyde, at least one diazotized compound, and anymixtures thereof.
 9. The method of claim 5 wherein said colorantconforms to the structure of Formula (II)

wherein R′ is selected from the group consisting of hydrogen, C₁-C₁₄alkoxy, and C₁-C₂₀ alkyl; wherein R″ is selected from the groupconsisting of hydrogen, C₁-C₄ alkyl groups; wherein R′″ is selected fromthe group selected from C₄-C₂₄ alkyl groups, phenyl, substituted phenyl,and any combinations thereof; and wherein x is from 1 to
 100. 10. Themethod of claim 5 wherein said colorant conforms to the structure ofFormula (III)

wherein R′ is selected from the group consisting of hydrogen and C₁-C₂₀alkyl; wherein R′ is selected from the group consisting of hydrogen,C₁-C₁₀ alkoxy, and C₁-C₂₀ alkyl; wherein R″ is selected from the groupconsisting of hydrogen, C₁-C₄ alkyl groups; wherein R′″ is selected fromthe group selected from hydrogen, C₄-C₂₄ alkyl groups, phenyl,substituted phenyl, and any combinations thereof; and wherein x is from1 to
 100. 11. The method of claim 5 wherein said colorant conforms tothe structure of Formula (IV)

wherein R′ is selected from the group consisting of hydrogen and C₁-C20alkyl; wherein R′ is selected from the group consisting of hydrogen,C₁-C₁₀ alkoxy, and C₁-C₂₀ alkyl; wherein R″ is selected from the groupconsisting of hydrogen, C₁-C₄ alkyl groups; wherein R′″ is selected fromthe group selected from hydrogen, C₄-C₂₄ alkyl groups; phenyl,substituted phenyl, and any combinations thereof; and wherein x is from1 to 100.